CA1195994A - Herbicidal n-haloacetyl-2-substituted-6-acylanilines - Google Patents
Herbicidal n-haloacetyl-2-substituted-6-acylanilinesInfo
- Publication number
- CA1195994A CA1195994A CA000391008A CA391008A CA1195994A CA 1195994 A CA1195994 A CA 1195994A CA 000391008 A CA000391008 A CA 000391008A CA 391008 A CA391008 A CA 391008A CA 1195994 A CA1195994 A CA 1195994A
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- carbon atoms
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- methyl
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
- A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
- A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
- A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
- A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
- A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/86—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/28—Radicals substituted by nitrogen atoms
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Compounds of the formula:
wherein X is halo; m and n are 0 or 1; R1 and R3 are hydrogen, alkyl or are joined to form a carbocyclic ring; R2 and R4 are hydrogen or alkyl;
R5 and R6 are hydrogen, alkyl or alkoxyalkyl; R7 is hydrogen, halo, nitro, alkoxy or alkyl; with certain excluded combinations, have herbicidal and growth- regulating activity, particularly against grassy weeds.
Compounds of the formula:
wherein X is halo; m and n are 0 or 1; R1 and R3 are hydrogen, alkyl or are joined to form a carbocyclic ring; R2 and R4 are hydrogen or alkyl;
R5 and R6 are hydrogen, alkyl or alkoxyalkyl; R7 is hydrogen, halo, nitro, alkoxy or alkyl; with certain excluded combinations, have herbicidal and growth- regulating activity, particularly against grassy weeds.
Description
01 HERBICIDAL N-HALOACETYL-2-SUBSTITUTED-6-ACYLAN~LINES
BACKGROU~ID OF THE INV~MTION
U.S. Patent No. 4,141,98g discloses 3~t~chloro-05 acetyl)-N-(2,6-dialkylphenylamino)-gamma-butyrolactones as fungicides.
U.S. Patent No. 4, 055,410 discloses substituted bromo and chloroacetamides as herbicides.
In Chem. Abs~r., 92:58400W (1980~, there are disclosed herbicidal 3 [3'~alkyl-2'-(N-haloacetylalkoxy~
methylamino)phenyl]-propionaldehyde 0,0-dialkyl acetals.
SUMMARY OF THE INVENTIO~
This invention relates to no~el N-haloacetyl-2-substituted 6-acylaniline compounds and methods o their lS use as herbicides and plant-growth regulators. It has now been found that the placement of certain acyl, ketal, oxime, hydroxyalkyl and alkoxyalkyl substituents on the 6~
position of N-haloacetyl-2-substitu~ed anilines results in compounds having herbicidal and plant~growth regulating activity. The compounds of the invention are particularly effective for pre-emergent treatment of grassy weeds.
DESCRIPTION OF THE IMVENTION
The compounds of the invention are represented by the formula:
R6O Rl R2 R7 N-CCH2X ~
~ O (C~l2jm (I) 3 0 ~ /\ O /~ R3 wherein X is halo; n and m are individually O
or or 1-~' ~5~
Rl and R3 are individually hydrogen or alkyl of 1 to 4 carbon atoms or Rl and R3 joined to form a carbocyclic ring con-taining 5 to 10 carbon atoms; R2 and R4 are individually hydrogen, alkyl of 1 to 4 carbon atoms, phenyl or phenyl substituted with 1 -to 4 halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 -to 4 carbon atoms or nitro groups;
R5 and R6 are individually hydrogen, alkyl of 1 to 4 carbon atoms or alkoxyalkyl of 2 to 6 carbon atoms; R7 is hyclrogen, halo, nitro, alkylthio of 1 to 4 carbon a-toms, alkoxy of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms; and provided that when R6 is hydrogen or alkyl of 1 to 4 carbon atoms, R is alkyl of 1 to 4 carbon atoms, and n is zero, then:
(1~ Rl, R2, R3 and R4 are not each all hydrogen; and ~ 2) if one of Rl or R2 is hydrogen and the other an alkyl group of 1 to 4 carbon atoms, and one of R3 and R4 is hydrogen, then the other is not the same alkyl group as Rl or R .
Representative Rl, R , R , R , R , R6 and R8 alkyl groups are methyl, ethyl, l-propyl, n-propyl, n-butyl, sec-bu-tyl, i-butyl.
Representative Rl-R carbocyclic linkages are -CH2C~2-, -(CH2)3-, -(CH2)4-, -(CH2~6-, and -(CH2)8-. Representative R and R phenyl groups are phenyl, p-chlorophenyl, 3,5-dichlorophenyl, 4-methyl~
phenyl, 4-methoxyphenyl. Preferably, Rl is alkyl o:E 1 to 4 carbon atoms and R2, R3 and R4 are hydrogen or alkyl of 1 -to 4 carbon atomsO
Represen-tative R5 and R6 alkoxyalky] groups are methoxy-methyl, methoxyethyl, ethoxyme-thyl, ethoxyethyl, methoxypropyl, ethoxybutyl, methoxypentyl~
Preferably, R5 ;s alkyl of I to 4 carbon atoms, and most prefer-ably, R is methyl. 6 Preferably, R is hydrogen.
Other representative R7 groups are chloro, bromo, fluoro, nitro, methoxy methylthio, ethoxy, propoxy, plopylthio, butoxy. Preferably, R7 is alkyl of 1 to 4 carbon atoms.
Representative X groups are chloro, bromo, fluoro, iodo. Prefer-ably, X is chloro.
BACKGROU~ID OF THE INV~MTION
U.S. Patent No. 4,141,98g discloses 3~t~chloro-05 acetyl)-N-(2,6-dialkylphenylamino)-gamma-butyrolactones as fungicides.
U.S. Patent No. 4, 055,410 discloses substituted bromo and chloroacetamides as herbicides.
In Chem. Abs~r., 92:58400W (1980~, there are disclosed herbicidal 3 [3'~alkyl-2'-(N-haloacetylalkoxy~
methylamino)phenyl]-propionaldehyde 0,0-dialkyl acetals.
SUMMARY OF THE INVENTIO~
This invention relates to no~el N-haloacetyl-2-substituted 6-acylaniline compounds and methods o their lS use as herbicides and plant-growth regulators. It has now been found that the placement of certain acyl, ketal, oxime, hydroxyalkyl and alkoxyalkyl substituents on the 6~
position of N-haloacetyl-2-substitu~ed anilines results in compounds having herbicidal and plant~growth regulating activity. The compounds of the invention are particularly effective for pre-emergent treatment of grassy weeds.
DESCRIPTION OF THE IMVENTION
The compounds of the invention are represented by the formula:
R6O Rl R2 R7 N-CCH2X ~
~ O (C~l2jm (I) 3 0 ~ /\ O /~ R3 wherein X is halo; n and m are individually O
or or 1-~' ~5~
Rl and R3 are individually hydrogen or alkyl of 1 to 4 carbon atoms or Rl and R3 joined to form a carbocyclic ring con-taining 5 to 10 carbon atoms; R2 and R4 are individually hydrogen, alkyl of 1 to 4 carbon atoms, phenyl or phenyl substituted with 1 -to 4 halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 -to 4 carbon atoms or nitro groups;
R5 and R6 are individually hydrogen, alkyl of 1 to 4 carbon atoms or alkoxyalkyl of 2 to 6 carbon atoms; R7 is hyclrogen, halo, nitro, alkylthio of 1 to 4 carbon a-toms, alkoxy of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms; and provided that when R6 is hydrogen or alkyl of 1 to 4 carbon atoms, R is alkyl of 1 to 4 carbon atoms, and n is zero, then:
(1~ Rl, R2, R3 and R4 are not each all hydrogen; and ~ 2) if one of Rl or R2 is hydrogen and the other an alkyl group of 1 to 4 carbon atoms, and one of R3 and R4 is hydrogen, then the other is not the same alkyl group as Rl or R .
Representative Rl, R , R , R , R , R6 and R8 alkyl groups are methyl, ethyl, l-propyl, n-propyl, n-butyl, sec-bu-tyl, i-butyl.
Representative Rl-R carbocyclic linkages are -CH2C~2-, -(CH2)3-, -(CH2)4-, -(CH2~6-, and -(CH2)8-. Representative R and R phenyl groups are phenyl, p-chlorophenyl, 3,5-dichlorophenyl, 4-methyl~
phenyl, 4-methoxyphenyl. Preferably, Rl is alkyl o:E 1 to 4 carbon atoms and R2, R3 and R4 are hydrogen or alkyl of 1 -to 4 carbon atomsO
Represen-tative R5 and R6 alkoxyalky] groups are methoxy-methyl, methoxyethyl, ethoxyme-thyl, ethoxyethyl, methoxypropyl, ethoxybutyl, methoxypentyl~
Preferably, R5 ;s alkyl of I to 4 carbon atoms, and most prefer-ably, R is methyl. 6 Preferably, R is hydrogen.
Other representative R7 groups are chloro, bromo, fluoro, nitro, methoxy methylthio, ethoxy, propoxy, plopylthio, butoxy. Preferably, R7 is alkyl of 1 to 4 carbon atoms.
Representative X groups are chloro, bromo, fluoro, iodo. Prefer-ably, X is chloro.
-2~-~' I
5~
01 Prererably ~ n and m are both zero.
The c:ompounds of the invention may be made according to the follo~ing scheme:
~_--NEICCH3 ~ ~~--NH2 ~ CH3CO~H (1) ( CH ~ ) nCR5 ( CH2 ) r~CR5 (Ia) (II) II + XCEI2CCl ~ ~\/ NHCCH2X ~ HCl ( 2 ) ( CH2 ) nCR5 ( I I I ) HO~CRl R2 "
25 III + (CH2)m H~ > ~NHCC~I2~ ~ H~O (3 (CH2)n O ~ R~
(IV) >< (CH2~m R5 ~
( IVa ) IVa ~ R6z Z=Br, Cl ) I ~ H~ ( 4 ) ~5~
01 The above reac~ions are conventional deacetyla-tion (1~, acetylation (2), l~etalization (3) and alkylation ~4) reactions and may be performed by known procedures.
In the case whereln R5 is hydrogenr my preferred oS method is as follo~s:
R7 R7 Rl ~ N02 + IV ~ N2 / ~ (5) (C~2)nc~o (CH2)nCH ~CH2)m ~ VI) R7 Rl VI ~/p~ ~ N~2 '~ - ~ R ~6) (CH~)ncH (C~2)m O ~ R3 (VII) ~ R7 Rl VII ~ XCH2CCl ~ NHCCH2 ~ 0--~ (7) (CH2)nCH\ (Cr~2)m
5~
01 Prererably ~ n and m are both zero.
The c:ompounds of the invention may be made according to the follo~ing scheme:
~_--NEICCH3 ~ ~~--NH2 ~ CH3CO~H (1) ( CH ~ ) nCR5 ( CH2 ) r~CR5 (Ia) (II) II + XCEI2CCl ~ ~\/ NHCCH2X ~ HCl ( 2 ) ( CH2 ) nCR5 ( I I I ) HO~CRl R2 "
25 III + (CH2)m H~ > ~NHCC~I2~ ~ H~O (3 (CH2)n O ~ R~
(IV) >< (CH2~m R5 ~
( IVa ) IVa ~ R6z Z=Br, Cl ) I ~ H~ ( 4 ) ~5~
01 The above reac~ions are conventional deacetyla-tion (1~, acetylation (2), l~etalization (3) and alkylation ~4) reactions and may be performed by known procedures.
In the case whereln R5 is hydrogenr my preferred oS method is as follo~s:
R7 R7 Rl ~ N02 + IV ~ N2 / ~ (5) (C~2)nc~o (CH2)nCH ~CH2)m ~ VI) R7 Rl VI ~/p~ ~ N~2 '~ - ~ R ~6) (CH~)ncH (C~2)m O ~ R3 (VII) ~ R7 Rl VII ~ XCH2CCl ~ NHCCH2 ~ 0--~ (7) (CH2)nCH\ (Cr~2)m
3 0 ~R3 (~'III) VIII T R6Z Z=Br, Cl~ I ~ HZ (~) 3'~
01 Reaction conditions for reactions (5), (7) and (8) are similar to those of reactions (3), (2~ and (4), respectively. Reac~ion (6~ may be performed under conven-tional hydrogenation conditions with platinum catalyst.
05 The compounds of the presen~ inven~ion are, in general, herbicidal and plant-growth regulating in both pre- and post~emergent applications, bu~ are particularly effective in pre-emergent applications. For pre emergent ~ control of undesirable vegetation, the herbicidal com-- 1~ pounds will be applied in herbicidally e~fective amounts to the locus or growth medium of the vegetation/ e.g., soil infested with seeds and/or seedlings of such vegeta-tion. Such application will inhibit the growth of or kill the seedsr germinating seeds and seedlings. For post-emergent applications) the herbicidal compounds will be applied directly ~o the foliage and other plant parts.
Generally, the herbicidal compounds of the invention are effective against weed grasses as well as broad-leaved weeds. Some may be selective with respect to the type of application and/or type of weedO The compounds of the invention are particularly effective as pre-emergent herbicides against weed grassesO
The compounds, when applied to growing plants above the ground in such an amount that the compounds will not kill beneficial plan~s, also show efficient plan~
growth regulating or retarding efects and may be advan-tageously employed, for example, to prevent or retard the growth of turf grassO
The compounds can be applied in any of a variety of compositions. In general, the compounds can be extended with a carrier material o the kind used and commonly referred to in the art such as inert solids, water and organic liquids.
The compounds will be included in such composi-tions in sufficient amount so that they can exert an 01 herbicidal or growth regulating effectO Usually romabout 0O5 to 95~ by weight of the compounds are included ; in such formulations.
Solid compositions can be made with inert 05 powders. The composi~ions thus can be homogeneous powders that can be used as such~ diluted with inert solids to form dusts, or suspended in a suitable liquid medium or spray application. The powders usually comprise the active ingredient admixed with minor amounts of condition-ing agent. Natural clays, either absorptive, such asattapulgite, or relatively non~absorptive, such as china clays, diatomaceous earth, synthetic fine silica, calcium silicate and other iner~ solid carriers of the kind con~
ventionally employed in powdered herbicidal compositions can be used. The active ingredient usually makes up from 0.5 to 90% of these powder compositions. The solids ordi-r narily should be very finely divided. For conversion o the powders to dusts~ talc, pyrophyllite, and the like, are customarily used.
Liquid compositions including the active compounds described ~bove can be prepared by admixing the compound with a suitable liquid diluent medium. Typical of the liquid media commonly employed are methanolr benzene, toluene, and the like. The active ingredient usually makes up from about 0.5 to 50% of these liquid compositions. Some of these compositions are designated to be used as such, and others to be extended with large quantities of water.
Compositions in the form of wettable powders or liquids can also include one or more surface-active agents, such as wetting, dispersing or emulsifying agents.
The surface~active agents cause the compositions of ~et-table powders or liquids to disperse or emulsify easily in water to give aqueous sprays.
01The surface active agents employed can be of the anionic~ cationic or nonionic type. They include, for example, sodium long-chain carboxylates, alkyl aryl sulfo~ates, sodium lauryl sulfate, polyethylene oxides, lignin sulfonates and other surface-active agents.
When used as a pre-emergent treatment, it is desirable to include a fertilizer, an insecticide, a fungicide or another herbicide.
The amount of compound or composition administered will vary with the particular plant part or plant growth medium which is to be contacted, the general location of application~ e., sheltered areas such as greenhouses, as compared to exposed areas such as fields -as well as the desired type of control. Generally~ for bo~h pre- and post~emergent herbicidal control, the com-pounds of the invention are applied at rates of 0.2 to 60 kg/ha, and the preferred rate is in the range 0.5 to 40 kg~ha. For plant growth regulating or retarding activity, it is essential to apply the oxime compounds at a concen-tration not so high as to kill the plants~ Therefore9 theapplication rates for plant growth regulating or retarding activity will generally be lower than the rates used for killing the plants. Generally, such rates vary from 0~1 to 5 kg/ha, and preferably from 0.1 to 3 kg/ha.
25Herbicidal tests on representative compounds of the invention were made using the following methods.
Pre-Emergent Herbicidal Test An acetone solution of the -test compound was prepared by mixing 375 mg of the compcund~ 118 mg of a nonionic surfactant and 18 ml of acetone. Ten ml of this solution was added to 40 ml of water to give the test solutionO
Seeds of the test vegetation were planted in a pot of soil and the test solution was sprayed uniformly onto the soil surface at a dose of 27.5 micrograms/cm2O
~8--01 The pot was watered and placed in a greenhouse. The pot was watered intermiktently and observed for seedling emergence, health of emerging seedlings, e~c., for a 3-week period. A~ the end of this period, the herbicidal 05 effectiveness of the compound was rated based on the physiological observations. A 0-to-100 scale was used, 0 representing no phytotoxicity, 100 representing complete kill. The results of these ~ests appear in Table I. The compounds were also tested at lower dosages on weeds and 0 crops. The results of these tests appear in Table II.
Post-Emergent ~erbicidal Test The tes~ compound was formulated in the same manner as described above for-the pre-emergent test. This formulation was uniformly sprayed on 2 similar pots of lS 24-day-old plants (approximately 15 to 25 plants per pot) at a dose of 27.5 micrograms/cm2. After the plants had dried, they were placed in a greenhouse and then watered intermittently at their bases J as needed. The plants were observed periodically or phytotoxic effects and physio-logical and morphological responses to the treatment.
After 3 weeks, the herbicidal effectiveness of the com-pound was rated based on these observations. A 0-to-100 scale was used, 0 representing no phytotoxicity and 100 representing complete ~ The results of these tests appear in Table I.
Plant-Growth Re~ulation ~est Four turf grass species shown in Table III were grown in rows in 6~5 x 9.5" pots to a height of 4 to 6", then were trimmed to a height of one inch. Each test com-pound was uniformly sprayed on the turf grass species at the test cncentrations. After 20 days in the greenhouse under normal watering and fertilization, each species was cut one inch above soil level and weiyhed. Weights are expressed as % grow~h inhibition compared to untreated check species. Four replicates were used per treatment.
I
5~
g 01 Example 1 - Preparation of N-Chloroacetyl 2-methyl-6-acetylaniline A. N-acetyl-2-methyl~6-acetylaniline (76.1 g) in water (300 ml), ethanol (300 ml), concentrated hydro-S chloric acid (300 ml) and concentrated sulfuric acid~lS ml) were refluxed for 24 hours, The solution was cooled and concentrated ammonium hydroxide was added to pH 10. The solution was extracted with dichloromethaneO
The extracts were dried (MgSO~) and stripped. 2-Methyl-ln 6-acetylaniline (49.3 y) was obtained as a tan solid.
B. 2-Methyl 6-acetylaniline (25 g) and pyridine (26~5 g) in 1 liter methylene chloride were cooled in an ice-acetone bath~ A solution of chloroacetyl chloride (37.9 g) in 100 ml methylene chloride was dripped in slowly. The solution was stirred at room temperature for 2 hours, washed with 10~ HCl~ 10~ NaOH, dried (MgSO4) and stripped. Yield. The title product as a white solid, MP
~8-89C.
Example 2 Preparation of 2,4-Dimethyl-2-(3'-methyl-2'-chloroacetamido-phenyl1 dioxolane N-chloroacetyl-2-methyl-6-acetylaniline (from Example 1), 4.51 g, 1,2-propanediol, 3.7 ml, and a dash of toluene sulfonic acid were combined in 50 ml toluene and refluxed. The distilled water by-product was collected in a Dean-Stark trap. After water ceased to distil, methyl-ene chloride was added and the mixture was extracted successively with bicarbonate solu~ion and water, ~hen dried (MgSO4) and evaporated to yield 3.3 g brown oil.
3~ The oil was purified on a silica gel column (Hexane:ethyl acetate eluant) to yield the title product (Compound No. 2 in Table A).
01Example 3 - Preparation of 2,4,4,5-Tetramethyl-2-(31-methyl 2'-chloroacetamido-phenyl) dioxolane The procedure of Example 2 was used employing 05 2-methyl-butane-2,3~diol instead of 1,2-propanediol.
The product was purified on a silica gel column to yield the ti~le product (Compound No. 3 in Table A).
Example 4 - Preparation of 2 Methyl-4-ethyl-2-(3'-methyl 102'-chloroacetamido~phenyl) dioxolane The procedure of Example 2 was used employing 1,2-butanediol instead of 1,2-propanediol.
The product was purified on a silica gel column to yield the title product (Compound No. 1 in Table A).
01 TABLE P, Compounds of the Formula:
0 5 ~= ~CE~3 ~g O Rl H3C ~R3 C
Analys~ s r~.p. C H N
No. R~ R2 R3 R4 C. CAL. FD. CAL. FD. CAL. FD.
C2H5 H E~ H Oil 60.5 61~4 6.8 7.5 4.7 4.5 2 CEI3 H K H Qil 59O 26 57 . 93 6 ~ 39 6 . 53 4 ~ 94 5 .16 3 CE~3 CH3 CK3 E~ oil 61.6 6û.l 7.1 7.2 4~5 4.5
01 Reaction conditions for reactions (5), (7) and (8) are similar to those of reactions (3), (2~ and (4), respectively. Reac~ion (6~ may be performed under conven-tional hydrogenation conditions with platinum catalyst.
05 The compounds of the presen~ inven~ion are, in general, herbicidal and plant-growth regulating in both pre- and post~emergent applications, bu~ are particularly effective in pre-emergent applications. For pre emergent ~ control of undesirable vegetation, the herbicidal com-- 1~ pounds will be applied in herbicidally e~fective amounts to the locus or growth medium of the vegetation/ e.g., soil infested with seeds and/or seedlings of such vegeta-tion. Such application will inhibit the growth of or kill the seedsr germinating seeds and seedlings. For post-emergent applications) the herbicidal compounds will be applied directly ~o the foliage and other plant parts.
Generally, the herbicidal compounds of the invention are effective against weed grasses as well as broad-leaved weeds. Some may be selective with respect to the type of application and/or type of weedO The compounds of the invention are particularly effective as pre-emergent herbicides against weed grassesO
The compounds, when applied to growing plants above the ground in such an amount that the compounds will not kill beneficial plan~s, also show efficient plan~
growth regulating or retarding efects and may be advan-tageously employed, for example, to prevent or retard the growth of turf grassO
The compounds can be applied in any of a variety of compositions. In general, the compounds can be extended with a carrier material o the kind used and commonly referred to in the art such as inert solids, water and organic liquids.
The compounds will be included in such composi-tions in sufficient amount so that they can exert an 01 herbicidal or growth regulating effectO Usually romabout 0O5 to 95~ by weight of the compounds are included ; in such formulations.
Solid compositions can be made with inert 05 powders. The composi~ions thus can be homogeneous powders that can be used as such~ diluted with inert solids to form dusts, or suspended in a suitable liquid medium or spray application. The powders usually comprise the active ingredient admixed with minor amounts of condition-ing agent. Natural clays, either absorptive, such asattapulgite, or relatively non~absorptive, such as china clays, diatomaceous earth, synthetic fine silica, calcium silicate and other iner~ solid carriers of the kind con~
ventionally employed in powdered herbicidal compositions can be used. The active ingredient usually makes up from 0.5 to 90% of these powder compositions. The solids ordi-r narily should be very finely divided. For conversion o the powders to dusts~ talc, pyrophyllite, and the like, are customarily used.
Liquid compositions including the active compounds described ~bove can be prepared by admixing the compound with a suitable liquid diluent medium. Typical of the liquid media commonly employed are methanolr benzene, toluene, and the like. The active ingredient usually makes up from about 0.5 to 50% of these liquid compositions. Some of these compositions are designated to be used as such, and others to be extended with large quantities of water.
Compositions in the form of wettable powders or liquids can also include one or more surface-active agents, such as wetting, dispersing or emulsifying agents.
The surface~active agents cause the compositions of ~et-table powders or liquids to disperse or emulsify easily in water to give aqueous sprays.
01The surface active agents employed can be of the anionic~ cationic or nonionic type. They include, for example, sodium long-chain carboxylates, alkyl aryl sulfo~ates, sodium lauryl sulfate, polyethylene oxides, lignin sulfonates and other surface-active agents.
When used as a pre-emergent treatment, it is desirable to include a fertilizer, an insecticide, a fungicide or another herbicide.
The amount of compound or composition administered will vary with the particular plant part or plant growth medium which is to be contacted, the general location of application~ e., sheltered areas such as greenhouses, as compared to exposed areas such as fields -as well as the desired type of control. Generally~ for bo~h pre- and post~emergent herbicidal control, the com-pounds of the invention are applied at rates of 0.2 to 60 kg/ha, and the preferred rate is in the range 0.5 to 40 kg~ha. For plant growth regulating or retarding activity, it is essential to apply the oxime compounds at a concen-tration not so high as to kill the plants~ Therefore9 theapplication rates for plant growth regulating or retarding activity will generally be lower than the rates used for killing the plants. Generally, such rates vary from 0~1 to 5 kg/ha, and preferably from 0.1 to 3 kg/ha.
25Herbicidal tests on representative compounds of the invention were made using the following methods.
Pre-Emergent Herbicidal Test An acetone solution of the -test compound was prepared by mixing 375 mg of the compcund~ 118 mg of a nonionic surfactant and 18 ml of acetone. Ten ml of this solution was added to 40 ml of water to give the test solutionO
Seeds of the test vegetation were planted in a pot of soil and the test solution was sprayed uniformly onto the soil surface at a dose of 27.5 micrograms/cm2O
~8--01 The pot was watered and placed in a greenhouse. The pot was watered intermiktently and observed for seedling emergence, health of emerging seedlings, e~c., for a 3-week period. A~ the end of this period, the herbicidal 05 effectiveness of the compound was rated based on the physiological observations. A 0-to-100 scale was used, 0 representing no phytotoxicity, 100 representing complete kill. The results of these ~ests appear in Table I. The compounds were also tested at lower dosages on weeds and 0 crops. The results of these tests appear in Table II.
Post-Emergent ~erbicidal Test The tes~ compound was formulated in the same manner as described above for-the pre-emergent test. This formulation was uniformly sprayed on 2 similar pots of lS 24-day-old plants (approximately 15 to 25 plants per pot) at a dose of 27.5 micrograms/cm2. After the plants had dried, they were placed in a greenhouse and then watered intermittently at their bases J as needed. The plants were observed periodically or phytotoxic effects and physio-logical and morphological responses to the treatment.
After 3 weeks, the herbicidal effectiveness of the com-pound was rated based on these observations. A 0-to-100 scale was used, 0 representing no phytotoxicity and 100 representing complete ~ The results of these tests appear in Table I.
Plant-Growth Re~ulation ~est Four turf grass species shown in Table III were grown in rows in 6~5 x 9.5" pots to a height of 4 to 6", then were trimmed to a height of one inch. Each test com-pound was uniformly sprayed on the turf grass species at the test cncentrations. After 20 days in the greenhouse under normal watering and fertilization, each species was cut one inch above soil level and weiyhed. Weights are expressed as % grow~h inhibition compared to untreated check species. Four replicates were used per treatment.
I
5~
g 01 Example 1 - Preparation of N-Chloroacetyl 2-methyl-6-acetylaniline A. N-acetyl-2-methyl~6-acetylaniline (76.1 g) in water (300 ml), ethanol (300 ml), concentrated hydro-S chloric acid (300 ml) and concentrated sulfuric acid~lS ml) were refluxed for 24 hours, The solution was cooled and concentrated ammonium hydroxide was added to pH 10. The solution was extracted with dichloromethaneO
The extracts were dried (MgSO~) and stripped. 2-Methyl-ln 6-acetylaniline (49.3 y) was obtained as a tan solid.
B. 2-Methyl 6-acetylaniline (25 g) and pyridine (26~5 g) in 1 liter methylene chloride were cooled in an ice-acetone bath~ A solution of chloroacetyl chloride (37.9 g) in 100 ml methylene chloride was dripped in slowly. The solution was stirred at room temperature for 2 hours, washed with 10~ HCl~ 10~ NaOH, dried (MgSO4) and stripped. Yield. The title product as a white solid, MP
~8-89C.
Example 2 Preparation of 2,4-Dimethyl-2-(3'-methyl-2'-chloroacetamido-phenyl1 dioxolane N-chloroacetyl-2-methyl-6-acetylaniline (from Example 1), 4.51 g, 1,2-propanediol, 3.7 ml, and a dash of toluene sulfonic acid were combined in 50 ml toluene and refluxed. The distilled water by-product was collected in a Dean-Stark trap. After water ceased to distil, methyl-ene chloride was added and the mixture was extracted successively with bicarbonate solu~ion and water, ~hen dried (MgSO4) and evaporated to yield 3.3 g brown oil.
3~ The oil was purified on a silica gel column (Hexane:ethyl acetate eluant) to yield the title product (Compound No. 2 in Table A).
01Example 3 - Preparation of 2,4,4,5-Tetramethyl-2-(31-methyl 2'-chloroacetamido-phenyl) dioxolane The procedure of Example 2 was used employing 05 2-methyl-butane-2,3~diol instead of 1,2-propanediol.
The product was purified on a silica gel column to yield the ti~le product (Compound No. 3 in Table A).
Example 4 - Preparation of 2 Methyl-4-ethyl-2-(3'-methyl 102'-chloroacetamido~phenyl) dioxolane The procedure of Example 2 was used employing 1,2-butanediol instead of 1,2-propanediol.
The product was purified on a silica gel column to yield the title product (Compound No. 1 in Table A).
01 TABLE P, Compounds of the Formula:
0 5 ~= ~CE~3 ~g O Rl H3C ~R3 C
Analys~ s r~.p. C H N
No. R~ R2 R3 R4 C. CAL. FD. CAL. FD. CAL. FD.
C2H5 H E~ H Oil 60.5 61~4 6.8 7.5 4.7 4.5 2 CEI3 H K H Qil 59O 26 57 . 93 6 ~ 39 6 . 53 4 ~ 94 5 .16 3 CE~3 CH3 CK3 E~ oil 61.6 6û.l 7.1 7.2 4~5 4.5
4 C2E~ H H C2H5 oil 62~7 67.3 7.4 3~0 4.3 4.4 CH3 H CH3 H 55--57 60.50 58.94 6.77 6.63 4.7 4.58 H H H H Oil -- - -- - 13.1* 11~,7*
*Chlorine ~5~
HE~BICIDA~ ACTIVITY @ 27.5 GAMMA/CM~
Pre/Post % Control No. L M _P C W O
l 60/0 70/0 55/~ -/10 100~6575/0 10 2 100/0 7~/0 75/0 100/20 100/35l00/1 3 .85/0 95/0 ~5/~ 100/0 100/090/0 L - Lambsquarter (Chenopodium album) M = Mustard ~Brassica arvensis~
P = Pigweed (~maranthus retroflexus) C = Crabgrass (Digitaria sanguinalis) W - Watergrass (Echinochola crusgalli) O = Wild Oats (Avenua fatua) 3~
a~ ~ o ~ o o ~--o o ~ c~
O
~o Ln o o Ln ~ o o o o o C~
a~ o a~ o ~ ~ o ~ ~n ~ ,, ~ ~
Q ~ O O O O ~ ~ O 11'1 CO ~0 c~ ~ ~ ~ o r- o #~ ~ o ~ r~ L
.
o o o Ln o o o o o o ~ ~ O
P~ ~I O~U~
~ ~ ~ O O ~ ~ O Ul O O ~ O O O ~
H H ~) L~ Ln ~ ~ 'P
H V -,, ~ ~!
~ ~ o o o 1~ o o In ~ o o Ln o o r . 'I 1. ¦ ~ ~ CO Lt~ O t~
Cl ~ .~ _~ ' o~ I
~; Z;
_~
l~ O ~ 00 ~ ~ ~ O O t~ ~ O
H ~ Cl~ ~ ~O O a~
1~ ~1 p~ rl o o o Ln o o Ln o o o o o o ~
O
O
U~ O
o ~ ~ o ~ ~ o ~ ,~ o I
O
Z; ~ ~
r-l Ln O Ln O
O O P 1 r-l ~J
~5~
-~4 TURF GRASS GROWTH INHIBITION
Contr~l ~5 No. ppm R F B C
400 0 5~ 56 21 6~ ~ 0 21 0 6 400 15 ~2 65 30 R = Ryegrass F = Cr~éping Red Fescue B = Bluegrass 20 C = Crabgrass
*Chlorine ~5~
HE~BICIDA~ ACTIVITY @ 27.5 GAMMA/CM~
Pre/Post % Control No. L M _P C W O
l 60/0 70/0 55/~ -/10 100~6575/0 10 2 100/0 7~/0 75/0 100/20 100/35l00/1 3 .85/0 95/0 ~5/~ 100/0 100/090/0 L - Lambsquarter (Chenopodium album) M = Mustard ~Brassica arvensis~
P = Pigweed (~maranthus retroflexus) C = Crabgrass (Digitaria sanguinalis) W - Watergrass (Echinochola crusgalli) O = Wild Oats (Avenua fatua) 3~
a~ ~ o ~ o o ~--o o ~ c~
O
~o Ln o o Ln ~ o o o o o C~
a~ o a~ o ~ ~ o ~ ~n ~ ,, ~ ~
Q ~ O O O O ~ ~ O 11'1 CO ~0 c~ ~ ~ ~ o r- o #~ ~ o ~ r~ L
.
o o o Ln o o o o o o ~ ~ O
P~ ~I O~U~
~ ~ ~ O O ~ ~ O Ul O O ~ O O O ~
H H ~) L~ Ln ~ ~ 'P
H V -,, ~ ~!
~ ~ o o o 1~ o o In ~ o o Ln o o r . 'I 1. ¦ ~ ~ CO Lt~ O t~
Cl ~ .~ _~ ' o~ I
~; Z;
_~
l~ O ~ 00 ~ ~ ~ O O t~ ~ O
H ~ Cl~ ~ ~O O a~
1~ ~1 p~ rl o o o Ln o o Ln o o o o o o ~
O
O
U~ O
o ~ ~ o ~ ~ o ~ ,~ o I
O
Z; ~ ~
r-l Ln O Ln O
O O P 1 r-l ~J
~5~
-~4 TURF GRASS GROWTH INHIBITION
Contr~l ~5 No. ppm R F B C
400 0 5~ 56 21 6~ ~ 0 21 0 6 400 15 ~2 65 30 R = Ryegrass F = Cr~éping Red Fescue B = Bluegrass 20 C = Crabgrass
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the formula:
wherein X is halo; n and m are independently 0 or 1; R1 and R3 are individually hydrogen or alkyl of 1 to 4 carbon atoms or R1 and R3 joined to form a carbocyclic ring containing 5 to 10 carbon atoms;
R2 and R4 are individually hydrogen, alkyl of 1 to 4 carbon atoms, phenyl or phenyl substituted with 1 to 4 halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or nitro groups; R5 and R6 are individually hydrogen, alkyl of 1 to 4 carbon atoms or alkoxyalkyl of 2 to 6 carbon atoms; R7 is hydrogen, halo, nitro, alkylthio of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms; and provided that when R6 is hydrogen or alkyl of 1 to 4 carbon atoms, R5 is alkyl of 1 to 4 carbon atoms, and n is zero, then:
(1) R1, R2, R3 and R4 are not each all hydrogen; and (2) if one of R1 or R2 is hydrogen and the other an alkyl group of 1 to 4 carbon atoms, and one of R3 and R4 is hydro-gen, then the other is not the same alkyl group as R1 or R2.
wherein X is halo; n and m are independently 0 or 1; R1 and R3 are individually hydrogen or alkyl of 1 to 4 carbon atoms or R1 and R3 joined to form a carbocyclic ring containing 5 to 10 carbon atoms;
R2 and R4 are individually hydrogen, alkyl of 1 to 4 carbon atoms, phenyl or phenyl substituted with 1 to 4 halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or nitro groups; R5 and R6 are individually hydrogen, alkyl of 1 to 4 carbon atoms or alkoxyalkyl of 2 to 6 carbon atoms; R7 is hydrogen, halo, nitro, alkylthio of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms; and provided that when R6 is hydrogen or alkyl of 1 to 4 carbon atoms, R5 is alkyl of 1 to 4 carbon atoms, and n is zero, then:
(1) R1, R2, R3 and R4 are not each all hydrogen; and (2) if one of R1 or R2 is hydrogen and the other an alkyl group of 1 to 4 carbon atoms, and one of R3 and R4 is hydro-gen, then the other is not the same alkyl group as R1 or R2.
2. A compound according to Claim 1 wherein m and n are 0.
3. A compound according to Claim 2 wherein R7 is alkyl of 1 to 4 carbon atoms.
4. A compound according to Claim 3 wherein R1 is alkyl of 1 to 4 carbon atoms and R2, R3 and R4 are individually hydrogen or alkyl of 1 to 4 carbon atoms.
5. A compound according to Claim 4 wherein X is chloro, R7 is methyl, R5 is alkyl of 1 to 4 carbon atoms and R6 is hydrogen.
6. The compound according to Claim 5 wherein R5 is methyl, R1 is ethyl and R2, R3 and R4 are hydrogen.
7. The compound according to Claim 5 wherein R5 and R1 are methyl and R2, R3 and R4 are hydrogen.
8. The compound according to Claim 5 wherein R5, R1, R2 and R3 are methyl and R4 is hydrogen.
9. A method of killing vegetation which comprises applying to said vegetation or its growth environment a herbicidally-effective amount of a compound defined in Claim 1.
10. A method for retarding plant growth which comprises applying to plants or their growth environment a plant-growth retarding amount of a compound of the formula defined in Claim 1.
11. A method for retarding the growth of Fescue, Bluegrass and Crabgrass which comprises applying to said plants or their growth environment a plant-growth retarding amount of a compound of the formula defined in Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US21161880A | 1980-12-01 | 1980-12-01 | |
| US211,618 | 1980-12-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1195994A true CA1195994A (en) | 1985-10-29 |
Family
ID=22787669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000391008A Expired CA1195994A (en) | 1980-12-01 | 1981-11-26 | Herbicidal n-haloacetyl-2-substituted-6-acylanilines |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS57120585A (en) |
| AU (1) | AU557690B2 (en) |
| BE (1) | BE891302A (en) |
| CA (1) | CA1195994A (en) |
| CH (1) | CH648304A5 (en) |
| DE (1) | DE3147155A1 (en) |
| FR (1) | FR2495152B1 (en) |
| GB (1) | GB2088380B (en) |
| IL (1) | IL64223A (en) |
| NL (1) | NL8105358A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3926898A1 (en) * | 1989-08-16 | 1991-02-21 | Thomae Gmbh Dr K | NEW 1,3-OXAZINE |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4244730A (en) * | 1979-07-02 | 1981-01-13 | Chevron Research Company | Herbicidal N-haloacetyl-2-alkyl-6-acylanilines |
-
1981
- 1981-11-06 IL IL64223A patent/IL64223A/en unknown
- 1981-11-23 FR FR8121872A patent/FR2495152B1/en not_active Expired
- 1981-11-26 CA CA000391008A patent/CA1195994A/en not_active Expired
- 1981-11-26 NL NL8105358A patent/NL8105358A/en not_active Application Discontinuation
- 1981-11-27 AU AU77957/81A patent/AU557690B2/en not_active Ceased
- 1981-11-27 DE DE19813147155 patent/DE3147155A1/en not_active Withdrawn
- 1981-11-30 CH CH7667/81A patent/CH648304A5/en not_active IP Right Cessation
- 1981-11-30 BE BE0/206702A patent/BE891302A/en not_active IP Right Cessation
- 1981-11-30 JP JP56192681A patent/JPS57120585A/en active Pending
- 1981-12-01 GB GB8136191A patent/GB2088380B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2088380B (en) | 1984-08-15 |
| DE3147155A1 (en) | 1982-07-29 |
| BE891302A (en) | 1982-03-16 |
| FR2495152B1 (en) | 1985-12-13 |
| IL64223A0 (en) | 1982-02-28 |
| AU7795781A (en) | 1982-06-10 |
| CH648304A5 (en) | 1985-03-15 |
| FR2495152A1 (en) | 1982-06-04 |
| JPS57120585A (en) | 1982-07-27 |
| IL64223A (en) | 1985-11-29 |
| AU557690B2 (en) | 1987-01-08 |
| GB2088380A (en) | 1982-06-09 |
| NL8105358A (en) | 1982-07-01 |
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